Gas Separation Process

ABSTRACT

A process for the separation of carbon dioxide from gas mixtures is disclosed in which a metal oxide sorbent, which is used to capture and release carbon dioxide, is recycled. The process incorporates the regeneration of the carbon dioxide capture capacity of the metal oxide to maintain a high capture capacity over many cycles. The regeneration involves hydrating the metal oxide and then heating the resulting metal hydroxide under a gas atmosphere that is effective to suppress the dehydration of the hydroxide so that dehydration occurs at an elevated temperature. The regeneration may also be used independently from the carbon dioxide separation process to produce, from a metal hydroxide, a metal oxide having an enhanced resistance to attrition and fragmentation.

TECHNICAL FIELD

The present invention relates to the separation of CO₂ from gasmixtures. More particularly, the invention relates to a CO₂ separationprocess in which a sorbent, which is used for absorbing the CO₂, isrecycled.

BACKGROUND ART

Addressing climate change is a large-scale global challenge. Currently,the world's economies annually emit approximately 26 gigatons of CO₂(GtCO₂) to the atmosphere from the combustion of fossil fuels. In theabsence of explicit efforts to address climate change, rising globalpopulations, higher standards of living, and increased demand for energycould result in as much as 9,000 gigatons of cumulative CO₂ beingemitted to the atmosphere from fossil fuel combustion over the nextcentury.

To stabilize CO₂ concentrations in the atmosphere “at a level that wouldprevent dangerous anthropogenic interference with the climate system” ascalled for in the United Nations Framework Convention on Climate Change,the cumulative amount of CO₂ released to the atmosphere over thiscentury would need to be held to no more than 2,600 to 4,600 GtCO₂—asubstantial reduction and a formidable challenge.

CO₂ Capture and Sequestration (CCS) is one of the most important of themitigation options. CCS involves the separation CO₂ from industrial andenergy-related sources, transport to a storage location and long-termisolation from the atmosphere. Technologies exist or are underdevelopment to capture CO₂ but their cost provides a significant barrierto widespread adoption. Transport to sites for alternative use orsequestration is provided by traditional compression and pipelinetechnologies. Other uses for captured CO₂ are for enhanced oil recovery,coal bed methane recovery and food and beverage processing. Currentexamples of CO₂ capture from process streams include the purification ofnatural gas and production of hydrogen-containing synthesis gas for themanufacture of ammonia, alcohols and synthetic liquid fuels.

The use of CaO (commonly known as burnt lime, lime or quicklime) as aregenerable sorbent for CO₂ capture has been proposed in severalprocesses dating back to the 19th century. The carbonation reaction ofCaO to separate CO₂ from hot gases (T>200° C.) and form CaCO₃ is veryfast. The regeneration of the sorbent by calcining the CaCO₃ into CaOand pure CO₂ is favored at T>900° C. (at a CO₂ partial pressure of 0.1MPa).

CaO_((s))+CO_(2(g))

CaCO_(3(s))  EQUATION 1

This carbonation-calcination cycle was successfully tested in a pilotplant (40 tonne d⁻¹) for the development of the acceptor coalgasification process using two interconnected fluidized beds (see G. P.Curran, C. E. Fink and E. Gorin, Adv. Chain. Ser. 69 (1967) 141-165).The use of the above cycle (Equation 1) for a post-combustion system wasfirst proposed by Shimizu et al. (IChemE., 77-A (1967) 62-70) andinvolved the regeneration of the sorbent in a fluidized ed, firing partof the fuel with O₂/CO₂ mixtures. The effective capture of CO₂ by CaOhas also been demonstrated in a small pilot fluidized bed (J. C.Abanades at al. AIChE. J. 50(7) (2004) 1614-1622).

A disadvantage of all of these processes is that the capacity of naturalsorhents (limestones and dolomites) to capture CO₂ typically diminishesrapidly, and a large make-up flow of sorbent (of the order of the massflow of fuel entering the plant) is required to maintain the CO₂ captureactivity in a capture-regeneration loop (J. C. Abanades, B. S. Rubin andE. J. Anthony Ind. Eng Chem. Res. 43 (2004) 3462-3466). Although thedeactivated sorbent may find application in th cement industry and thesorbent cost is low, a range of methods to enhance the activity ofcalcium-based CO₂ sorbents have been pursued.

Abanades and co-workers have published several papers examining theCaO/CO₂ system employing sequential calcination and carbonation steps(see: J. C. Abanades at al. “In-situ capture of CO₂ in a fluidized bedcombustor” Proc. 17th Int. Fluidized Bed Combustion Conference,Jacksonville, Fla., May 2003; J. C. Abanades and D. Alvarez Energy Fuels17 (2003) 308-315; and J. C. Abanades Chem. Eng. J. 90 (2002) 303-306).They reported that the capacity of limestone to be recarbonated fallscontinuously with the number of cycles. After examining data from anumber of researchers who used different limestones, different particlesizes (10 μm to 10 mm) and a range of treatment temperatures (750 to1060° C.), they concluded that there was uniformity in the conversiondisplayed by equivalent data, which defined a generalized correlation.The correlation relating the conversion capacity to the number of thecycle is given as:

X _(N) f _(m) ^(N)(1−f _(W))+f _(W)  (1)

where N is the number of the cycle (for uncalcined limestone N=0), andf_(m) is the fractional loss in conversion from the previous cycle,assumed constant with N. The parameter f_(w) is the theoretical residualcapacity after infinite cycles. From their collection of data, Abanadesand Alvarez (Energy Fuels 17 (2003) 308-315) assigned values of 0.77 tof_(m) and 0.17 to f_(w).

WO 2005/046863 describes a process for reactivating lime-based sorbentsfor multiple CO₂ capture cycles during the fluidized bed oxidation ofcombustion fuels by hydrating the lime after each calcination or byshocking the lime with pure CO₂.

Fennell et al. (J. Energy Inst. 80 (2007) 116-119) have shown that thedrop in CO₂ absorption capacity when limestone is subject to at least 10calcination-carbonation cycles is partially recovered when the lime isexposed to water vapor at ambient temperatures overnight. They alsoobserved that the limestone underwent substantial attrition which theyattributed to the regeneration by the hydration step.

The reactivity and durability of calcium-based sorbents for CO₂absorption during repetitive carbonation-calcination reactions atdifferent pressures in a laboratory-scale horizontal-tube reactor hasbeen investigated (K. Kuramoto et al Ind. Eng. Chem. Res. 42 (2003)975-981). It was found that the sorbents were significantly deactivatedwith respect to CO₂ absorption by high-temperature calcination treatmentas a result of sintering and crystal growth. As a consequence, their CO₂absorption capacity decreases with cycle number in repetitivecalcination-carbonation reactions under both atmospheric and pressurizedconditions. For at least seven cycles hydration treatment was effectivein reactivating these sorbents. Also, the durability of the sorbents inrepetitive CO₂ sorption was recovered by hydration treatment both atambient temperature and pressure, and at elevated pressure at 200° C.However, at elevated pressure, the sorbents melted in repetitivecalcination-hydration-carbonation reactions at 923 K and 973 K, mostlikely because of eutectics in the CaO—Ca(OH)₂—CaCO₃ ternary system.

Accordingly, it is an object of the present invention to go some way toavoiding the above disadvantages or to at least provide the public witha useful choice.

Other objects of the invention may become apparent from the followingdescription which is given by way of example only.

Any discussion of documents, acts, materials, devices, articles or thelike which has been included in the present specification is solely forthe purpose of providing a context for the present invention. It is notto be taken as an admission that any or all of these matters form partof the prior art base or were common general knowledge in the fieldrelevant to the present invention as it existed before the prioritydate.

SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (h) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream comprising    CO₂ to a temperature that is higher than the normal decomposition    temperature for the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (1); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i),

In a second aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream comprising    CO₂ to a temperature that is higher than the normal decomposition    temperature for the metal hydroxide, and to a temperature and for a    time and at a concentration of CO₂ effective to suppress the    dehydration of the metal hydroxide and reduce the attrition and    fragmentation rates, compared to those that would otherwise occur,    of the metal oxide formed upon dehydration of the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In a third aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) contacting a metal oxide with the first gas stream to carbonate    the metal oxide and form a metal carbonate;-   (b) calcining the metal carbonate to regenerate the metal oxide and    produce a product gas stream comprising CO₂;-   (c) repeating steps (a) and (b) using the metal oxide regenerated in    step (b);-   (d) contacting the metal oxide regenerated in step (b) with water to    form a metal hydroxide;-   (e) heating the metal hydroxide in a second gas stream comprising    CO₂;-   (f) dehydrating the metal hydroxide in a third gas stream to    regenerate the metal oxide; and-   (g) repeating steps (a) to (f) using the metal oxide regenerated in    step (f).

In a fourth aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) Calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream, wherein the    second gas stream comprises a gas effective to suppress the    dehydration of the metal hydroxide, to a temperature that is higher    than the normal decomposition temperature for the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In a fifth aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream, wherein the    second gas stream comprises a gas effective to suppress the    dehydration of the metal hydroxide, to a temperature that is higher    than the normal decomposition temperature for the metal hydroxide,    and to a temperature and for a time and at a concentration of the    gas effective to suppress the dehydration of the metal hydroxide and    reduce the attrition and fragmentation rates, compared to those that    would otherwise occur, of the metal oxide formed upon dehydration of    the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In a sixth aspect, the present invention provides a process forproducing a metal oxide by dehydrating a metal hydroxide, the processcomprising heating the metal hydroxide in a gas stream, wherein the gasstream comprises a gas effective to suppress the dehydration of themetal hydroxide, to a temperature higher than the normal dehydrationtemperature for the metal hydroxide, and dehydrating the metal hydroxideto obtain the metal oxide.

In a seventh aspect, the present invention provides a process forrestoring the ability of a metal oxide to react with CO₂, wherein themetal oxide is used in a cyclic process, wherein the metal oxide isreacted with CO₂ to form a metal carbonate and the metal carbonate iscalcined to regenerate the metal oxide, the process comprising the stepsof:

-   (a) contacting the metal oxide with water to form a metal hydroxide;-   (b) heating the metal hydroxide in a gas stream, wherein the gas    stream comprises a gas effective to suppress the dehydration of the    metal hydroxide, to a temperature higher than the normal dehydration    temperature for the metal hydroxide; and-   (c) dehydrating the metal hydroxide to regenerate the metal oxide.

The present invention also provides apparatus adapted to perform aprocess of the invention.

This invention may also be said broadly to consist in the parts,elements and features referred to or indicated in the specification ofthe application, individually or collectively, and any or allcombinations of any two or more said parts, elements or features, andwhere specific integers are mentioned herein which have knownequivalents in the art to which this invention relates, such knownequivalents are deemed to be incorporated herein as if individually setforth.

Unless otherwise specified, the gas concentrations in this specificationare expressed as moi.

The term “comprising” as used in this specification means “consisting atleast in part of”. When interpreting each statement in thisspecification that includes the term “comprising”, features other thanthat or those prefaced by the term may also be present. Related termssuch as “comprise” and “comprises” are to be interpreted in the samemanner.

The term “and/or” as used in this specification means “and”, or “or”, orboth.

It is intended that reference to a range of numbers disclosed herein(for example, 1 to 10) also incorporates reference to all rationalnumbers within that range (for example, 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5,7, 8, 9 and 10) and also any range of rational numbers within that range(for example, 2 to 8, 1.5 to 5.5 and 3.1 to 4.7) and, therefore, allsub-ranges of all ranges expressly disclosed herein are hereby expresslydisclosed. These are only examples of what is specifically intended andall possible combinations of numerical values between the lowest valueand the highest value enumerated are to be considered to be expresslystated in this application in a similar manner.

Although the present invention is broadly as defined above, thosepersons skilled in the art will appreciate that the invention is notlimited thereto and that the invention also includes embodiments ofwhich the following description gives examples.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will now be described with reference to the Figures inwhich:

FIG. 1 shows a schematic diagram of a fluidized bed reactor useful for areaction cycling regime using CaO as a CO₂ sorbent;

FIG. 2 shows a calcination-hydration-dehydration-carbonation reactioncycling regime using CaO as a CO₂ sorbent;

FIG. 3 shows the temperature profile as a function of time for acalcination-hydration-dehydration-carbonation reaction cycle using CaOas a CO₂ sorbent;

FIG. 4 shows a calcination-carbonation reaction cycling regime using CaOas a CO₂ sorbent with intermittent hydration;

FIG. 5 shows the temperature profile as a function of time for acalcination-carbonation reaction cycle using CaO as a CO₂ sorbent;

FIG. 6 shows the cumulative fragmentation for CaO as a CO₂ sorbent overseveral calcination-hydration-dehydration-carbonation reaction cyclesand calcination-carbonation reaction cycles with intermittent hydration;

FIG. 7 shows a calcination-carbonation reaction cycling regime using CaOas a CO₂ sorbent with intermittent hydration and dehydration under CO₂;

FIG. 8 shows the CO₂ capture activity for CaO as a CO₂ sorbent overseveral calcination-carbonation reaction cycles with intermittenthydration and calcination-carbonation reaction cycles with intermittenthydration and dehydration under CO₂;

FIG. 9 shows the variation of temperature and the water vapor pressureover a bed of Ca(OH)₂ as a function of time during the heating of thebed under N₂;

FIG. 10 shows the variation of temperature and the water vapor pressureover a bed of Ca(OH)₂ as a function of time during the heating of thebed under N₂ and CO₂ (20%);

FIG. 11 shows the variation of temperature and the water vapor pressureover a bed of Ca(OH)₂ and temperature as a function of time during theheating of the under N₂ and CO₂ (20%) followed by further heating underN₂; and

FIG. 12 shows the dependence of Ca(OH)₂ dehydration temperature on CO₂concentration.

DETAILED DESCRIPTION OF THE INVENTION

The tendency for lime to undergo structural changes during repeatedcarbonation-calcination cycles significantly reduces its capacity toabsorb CO₂ and reduces the efficacy and economic efficiency ofconventional CO₂ absorption processes in which a lime sorbent isrecycled.

Hydrating lime at least partially restores its capacity to absorb CO₂which otherwise reduces with repeated carbonation-calcination cycles.However, hydrating lime induces structural changes in the material.These changes eventually lead to a weakening of the lime, resulting insignificantly increased attrition and fragmentation of the lime sorbentin subsequent carbonation-calcination cycling, especially in fluidizedbed reactors. This means that conventional hydration is ineffective inreducing the loss of CO₂ absorption activity duringcarbonation-calcination cycling, because the CO₂ absorption activity islimited by losses to attrition and fragmentation.

The present invention relates to a process for regenerating the CO₂capture capacity of a metal oxide that is used in a cyclic CO₂ captureprocess. The present invention further relates to a cyclic process thatuses a metal oxide to capture and release CO₂ and that intermittentlyregenerates the CO₂ capture capacity of the metal oxide to maintain ahigh capture capacity, with reduced rates of attrition andfragmentation, over many cycles. The present invention also relates to aprocess for producing a metal oxide from a metal hydroxide, wherein theproduct metal oxide has an enhanced resistance to attrition andfragmentation.

More specifically, in a first aspect, the present invention provides aprocess for separating CO₂ from a first gas stream comprising CO₂, theprocess comprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream comprising    CO₂ to a temperature that is higher than the normal decomposition    temperature for the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In as second aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;    calcining the metal carbonate regenerated in step (b) to regenerate    the metal oxide and produce a second product gas stream comprising    CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   heating the metal hydroxide in a second gas stream comprising CO₂ to    a temperature that is higher than the normal decomposition    temperature for the metal hydroxide, and to a temperature and for a    time and at a concentration of CO₂ effective to suppress the    dehydration of the metal hydroxide and reduce the attrition and    fragmentation rates, compared to those that would otherwise occur,    of the metal oxide formed upon dehydration of the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In a third aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) contacting a metal oxide with the first gas stream to carbonate    the metal oxide and form a metal carbonate;-   (b) calcining the metal carbonate to regenerate the metal oxide and    produce a product gas stream comprising CO₂;-   (c) repeating steps (a) and (b) using the metal oxide regenerated in    step (b);-   (d) contacting the metal oxide regenerated in step (b) with water to    form a metal hydroxide;-   (e) heating the metal hydroxide in a second gas stream comprising    CO₂;-   (f) dehydrating the metal hydroxide in a third gas stream to    regenerate the metal oxide; and-   (g) repeating steps (a) to (f) using the metal oxide regenerated in    step (i).

Metal Oxide

A number of metal oxides can be carbonated to form the correspondingmetal carbonate that, in turn, can be calcinated to regenerate the metaloxide. Any of these oxides may be used as the CO₂ sorbent in a processof the invention.

In one embodiment, the metal oxide is selected from the group consistingof: alkali metal oxides; alkaline earth metal oxides; first rowtransition metal oxides; aluminum oxide; lead oxide; and mixtures of anytwo or more thereof. In another embodiment, the metal oxide is selectedfrom the group consisting of alkaline earth metal oxides; zinc oxide;manganese oxide; nickel oxide; copper oxide; lead oxide; and mixtures ofany two or more thereof. In a preferred embodiment, the metal oxide isan alkaline earth metal oxide. In another preferred embodiment, themetal oxide is selected from: CaO; MgO; and mixtures thereof. A metaloxide within this embodiment may be formed by calcining dolomite(calcium magnesium carbonate, CaMg(CO₃)₂). In another preferredembodiment, the metal oxide is CaO. A metal oxide within this embodimentmay be formed by calcining limestone (calcium carbonate, CaCO₃).

The invention also contemplates embodiments in which the startingmaterial for the third embodiment is a metal carbonate such that theprocess comprises a preliminary step, before step (a), of calcining themetal carbonate to form the metal oxide.

Calcination

Any calcination process may be utilized to calcine the metal carbonateto regenerate the metal oxide and produce a stream of CO₂. The selectionof the temperature at which the metal carbonate is calcined will dependon the pressure, particularly on the partial pressure of CO₂. In oneembodiment, the carbonate is calcined by heating to a temperaturebetween about 700° C. and about 1100° C. under a partial pressure of CO₂that is below the equilibrium pressure. Under these conditions, thecarbonate rapidly decomposes to release a stream of CO₂.

The various product gas streams comprising CO₂ gas obtained uponcalcination of the metal carbonate may be suitable for directutilization or, if necessary, may be further purified, for example byscrubbing to remove particulate matter. In one embodiment, the productgas streams comprise substantially pure CO₂.

Carbonation

Gas streams comprising CO₂ are well-known in the art and include, butare not limited to: flue gas from combustion processes; syngas ofdifferent compositions produced by gasifiers; gas outputs from cementkilns and steel production; gas outputs from ammonia synthesis; gasoutputs from various biological reactors, including fermenters anddigesters; some natural gas; and air. In some embodiments, the gasstream comprising CO_(z) is a post-combustion gas stream and in otherembodiments, the gas stream is a pre-combustion gas stream.

In one embodiment, the first gas stream comprises CO₂ in a concentrationfrom about 5% to about 100%. However, the invention is not limitedthereto and the first gas stream may comprise CO₂ in a concentrationthat is outside this range. For example, the first gas stream maycomprise ambient air, in which the CO₂ concentration is about 380 ppm.

The selection of the temperature at which the metal oxide is contactedwith a gas stream comprising CO₂ to carbonate the metal oxide and formthe metal carbonate will depend on the pressure, particularly on thepartial pressure of CO₂. Typically, the metal oxide is contacted withthe gas stream comprising CO₂ at a temperature between about 300° C. andabout 950° C.

However, temperatures outside this range may be used in someembodiments. In particular, higher temperatures may be used where thepartial pressure of CO₂ is sufficiently high,

In one embodiment, the metal oxide is carbonated at a temperature from600° C. to 800° C. The length of time that the metal oxide is contactedwith the gas stream comprising CO₂ will also depend on the pressure andtemperature of the gas stream. In one embodiment, the metal oxide iscontacted with the gas stream comprising CO₂ for 5 minutes to 60minutes. Time outside this range may be used in other embodiments.

In those embodiments wherein the first gas stream is at atmospheric orlow pressure and high temperature—for example, in post-combustionapplications, and gas outputs from cement kilns—the temperature istypically between about 450° C. and about 800° C. In those embodimentswherein the first gas stream is at high pressure and hightemperature—for example, in pre-combustion applications and gas outputsfrom gasifiers—the temperature is typically between about 550° C. andabout 950° C.

In those embodiments wherein the first gas stream is at lowtemperature—for example, in air, and gas outputs from biologicalreactors such as fermenters and digesters—the metal oxide may becontacted with the first gas stream at ambient temperature, or the firstgas stream may be compressed and/or heated prior to contacting the metaloxide.

Apparatus

Suitable apparatus for performing the process of the invention arewell-knovm. The various process steps may be performed at ambientpressure or, in some embodiments, one or more steps may be performed atelevated or reduced pressure.

The metal oxide may be contacted with a gas stream comprising CO₂ orwith water using a suitable gas-solid contact reactor.

In one embodiment, the gas-solid contact reactor comprises a mobilesolid phase. In a preferred embodiment, the gas-solid contact reactorcomprises a fluidized or moving bed. In some embodiments, a fluidized ormoving bed system may be preferred to improve the gas-solid contact;facilitate mass transfer in and out of the solid; improve the heattransfer properties of the solid; and facilitate the transfer of thesolid from one reaction (reactor) to another.

Accordingly, in a preferred embodiment, at least one step of a processof the invention is performed in one or more fluidized or moving bed. Inanother preferred embodiment, all of the steps are performed in one ormore fluidized or moving bed.

It is well-known that the interparticle collisions in fluidized andmoving bed systems cause mechanical deterioration of the solid and theproduction of fines that may be elutriated from the system. Such finesmay result in a loss of still active sorbent or require the use of dustseparation units. In addition, the presence of fines may makefluidization of the solid more difficult to achieve.

Calcium oxide can be chemically activated for use as a CO₂ sorbent byhydration with water between calcination and carbonation in a cyclicprocess. However, hydration of calcium oxide is disadvantageous for itsphysical properties. Repeated cycling in this manner(carbonation-calcination-hydration-dehydration) causes the material tovesiculate, expand and become very brittle. Hydration alone is,therefore, insufficient to maintain calcium oxide as a viable CO₂sorbent over many tens of cycles in a fluidized bed reactor.

Accordingly, the present invention provides a sequence of stepsinvolving hydration for sorbent activation and thermal treatment of theresulting hydroxide to enhance particle resistance to attrition andfragmentation in the harsh conditions of a fluidized bed.Advantageously, each of the steps in the process of the presentinvention may be performed in the same fluidized bed, thereby avoidingthe inefficiencies associated with moving the sorbent material between anumber of different reactors. However, the invention is not limitedthereto and embodiments in which the sorbent material is moved betweentwo or more reactors either between or during the various steps of theprocess are also contemplated.

The invention also includes embodiments in which the sorbent material isheld in several reactors and the mass flows into and out of the reactorsare controlled to achieve continuous processing of the first gas streamcomprising CO₂.

The steps used in the present invention reduce the need to addadditional CO₂ sorbent. However, if necessary, fresh sorbent can beadded to replace the amount lost from the system as fines or otherwiselost through side reactions such as reaction with other components inthe gas stream.

In one embodiment of the first and second aspects, the number of timessteps (b) and (c) are repeated in step (d) is from 1 to 20. In anotherembodiment, the number of times steps (b) and (c) are repeated in step(d) is from 2 to 4.

In one embodiment of the first and second aspects, the number of timessteps (e) to (g) are repeated in step (h) is from 1 to 20. In anotherembodiment, the number of times steps (e) to (g) are repeated in step(h) is from 1 to 4.

In a preferred embodiment of the first and second aspects, step (h) isomitted.

In one embodiment of the first and second aspects, the number of timessteps (c) to (i) are repeated in step (j) is from 1 to 20. In anotherembodiment, the number of times steps (e) to (i) are repeated in step(j) is from 1 to 4.

In a preferred embodiment of the first and second aspects, step (j) isomitted.

In one embodiment of the third aspect, the number of times steps (a) and(b) are repeated in step (c) is from 1 to 20. In another embodiment, thenumber of times steps (a) and (b) are repeated in step (c) is from 2 to4.

In one embodiment, the amount of metal oxide retained in the fluidizedbed is at least about 85% of the initial amount after 75 calcinations.Preferably, the amount of metal oxide retained in the fluidized bed isat least about 90% of the initial amount after 75 calcinations.

In one embodiment, the metal oxide retains an average CO₂ absorptioncapacity of at least about 40%, measured with respect to the initialcapacity, after 75 calcinations. Preferably, the metal oxide retains anaverage CO₂ absorption capacity of at least about 55% after 75calcinations.

In one embodiment, the metal oxide retains an average CO₂ absorptioncapacity of at least about 315 g CO₂/kg metal oxide after 75calcinations. Preferably, the metal oxide retains an average CO₂absorption capacity of at least about 430 g CO₂/kg metal oxide after 75calcinations.

Hydration

The metal oxide may be contacted with water that is either in the liquidphase or is water vapor. In a preferred embodiment, the metal oxide iscontacted with water vapor. In some embodiments, the contacting isperformed at elevated pressure.

The metal oxide is typically contacted with water at a partial pressureabove the equilibrium pressure for the formation of the metal hydroxideat the selected hydration temperature. In one embodiment, the metaloxide is contacted with water vapor at an absolute humidity from 5% to100%. In a preferred embodiment, the absolute humidity is from 30% to43%.

In one embodiment, the metal oxide is contacted with water vapor at atemperature from 100° C. to 700° C. In a preferred embodiment, thetemperature is from 100° C. to 450° C., more preferably from 100° C. to400° C., more preferably from 150° C. to 400° C., more preferably from280° C. to 380° C.

The metal oxide is typically contacted with water until the hydrationreaction is at least substantially complete.

In one embodiment, the metal hydroxide is maintained in the presence ofthe water vapor for a time from 5 to 60 minutes. Preferably, the time isfrom 15 to 25 minutes.

During the sequence of reactions, hydration is followed by heating themetal hydroxide in the presence of CO₂. Therefore, in some embodiments,there will be some overlap between these process steps, such that CO₂ ispresent during the hydration of the metal oxide.

Accordingly, in one embodiment, CO₂ is added to the water vapor afterthe metal oxide has partially or fully hydrated. In one embodiment, thewater vapor further comprises CO₂ in the range from 0% to 75%. Inanother embodiment, the water vapor further comprises CO₂ in the rangefrom 0% to 20%.

Dehydration

Conventionally, a metal hydroxide may be dehydrated by heating to atemperature between about 400° C. and about 700° C. under a water vaporpressure that is below the equilibrium vapor pressure for the hydroxideat the selected pressure. Alternatively, the metal hydroxide may bedehydrated at a lower temperature, for example down to about 100° C., byreducing the pressure at which the dehydration takes place.

As set out above, the sequence of process steps disclosed hereinincludes thermal treatment of the metal hydroxide to enhance theresistance of the sorbent particles to attrition and fragmentation inthe harsh conditions of a fluidized bed. This thermal treatment involvesheating the metal hydroxide in a second gas stream comprising CO₂. Insome embodiments, this treatment may be performed at elevated pressure.

Advantageously, heating the metal hydroxide in the second gas streamcomprising CO₂ enables the metal hydroxide to be heated to a highertemperature than that at which dehydration would be expected tooccur—the normal decomposition temperature. Heating the metal hydroxidein an atmosphere comprising CO₂ results in a thermodynamically unstablemetal hydroxide.

Accordingly, in one embodiment of the third aspect, step (e) comprisesheating the metal hydroxide to a temperature that is higher than thenormal decomposition temperature for the metal hydroxide.

The term “normal decomposition temperature” as used in thisspecification means the temperature at which dehydration of the metalhydroxide is observed to occur under an inert atmosphere (such as a N₂atmosphere) in equivalent apparatus and under equivalent processconditions. Such process conditions may include the water vaporpressure, total gas flow, reactor size and type (for example, fluidizedor static bed), sorbent amount, sorbent particle size, sorbent history,heat flow etc. Generally, dehydration will be observed when the metalhydroxide loses water at a rate of about 0.5% w/w per minute. Thosepersons skilled in the art can readily determine the normaldecomposition temperature of the metal hydroxide without undueexperimentation.

For example, FIG. 9 shows that the normal decomposition temperature ofCa(OH)₂ in a stream of N₂ is about 445° C. in the apparatus and underthe conditions described in the Examples. As shown in FIG. 12, thatdecomposition temperature in the same apparatus and under equivalentprocess conditions increases to: 529° C. for a 12.5% CO₂/N₂ mixture;543° C. for a 25% CO₂/N₂ mixture; 611° C. for a 37.5% CO₂/N₂ mixture;619° C. for a 70% CO₂/N₂ mixture; and 620° C. for 100% CO₂ gas.

The subsequent dehydration of the thermodynamically unstable metalhydroxide produces a metal oxide that has lower attrition andfragmentation rates during subsequent cycling in a fluidized bed reactorthan the metal oxide produced by conventional dehydration. The increasedmechanical strength of the metal oxide is thought to arise frommaintaining the metal hydroxide in a thermodynamically unstable state,at temperatures higher than normal metal hydroxide decompositiontemperature. It is thought that, at these temperatures, a process akinto annealing occurs, where the strains and crystal defects formed duringhydration of the metal oxide are healed. The extent of healing may,therefore, be proportional to both the temperature and the time spent bythe metal hydroxide in the thermodynamically unstable state.

In one embodiment, the second gas stream comprising CO₂ is the same asthe first gas stream. However, the invention also includes embodimentsin which the second as stream comprises a different concentration ofCO₂. For example, the first gas stream may be enriched or depleted inCO₂ to provide the second stream. Alternatively, the second gas streammay be substantially pure CO₂.

Advantageously, the various product gas streams comprising CO₂ gasobtained upon calcination of the metal carbonate may be recycled toprovide the CO₂ used in the second gas stream. Accordingly, in apreferred embodiment, the second gas stream comprises CO₂ from the firstand/or second product gas streams.

In one embodiment, the second gas stream comprises 5% to 1.00% CO₂. In apreferred embodiment, the second gas stream comprises 20% to 100% CO₂,more preferably 30% to 100% CO₂, more preferably 37.5% to 100% CO₂.

In another preferred embodiment, the second gas stream comprises a CO₂concentration selected from: 12.5%; 25%; 37.5%; 70% and 100%.

During the sequence of reactions, heating the metalhydroxide in thepresence of CO₂ follows hydration. Therefore, in some embodiments, therewill be some overlap between these process steps, such that water vaporis present during the heating of the metal hydroxide. Accordingly, inone embodiment, the second gas stream comprising CO₂ further compriseswater vapor.

In one embodiment, the metal hydroxide is heated to a temperature thatis at least about 10° C. higher than the normal decompositiontemperature for the metal hydroxide. In a preferred embodiment, thetemperature is at least about 20° C. higher than the normaldecomposition temperature for the metal hydroxide; at least about 30° C.higher; at least about 40° C. higher; at least about 50° C. higher; atleast about 60° C. higher; at least about 70° C. higher; at least about80° C. higher; at least about 90° C. higher; at least about 100° C.higher; at least about 110° C. higher; at least about 120° C. higher; atleast about 130° C. higher; at least about 140° C. higher; at leastabout 150° C. higher; at least about 160° C. higher; or at least about170° C. higher.

In a preferred embodiment, the metal hydroxide is heated to atemperature that is at least about 50° C. higher than the normaldecomposition temperature for the metal hydroxide.

In other embodiments, the temperature difference between the normaldecomposition temperature of the metal hydroxide and the temperature towhich the metal hydroxide is heated is selected from: 10° C.; 15° C.;20° C.; 25° C.; 30° C.; 35° C.; 40° C.; 45° C.; 50° C.; 55° C.; 60° C.;65° C.; 70° C.; 75° C.; 80° C.; 85° C.; 90° C.; 95° C.; 100° C.; 105°C.; 110° C.; 115° C.; 120° C.; 125° C.; 130° C.; 135° C.; 140° C.; 145°C.; 150° C.; 155° C.; 160° C.; 165° C.; 170° C.; 175° C.; and anysubgroup thereof.

The upper limit of the temperature to which the metal hydroxide isheated is that temperature at which the metal hydroxide inevitably loseswater to form the metal oxide.

The time the metal hydroxide spends in the thermodynamically unstablestate is determined by the heating rate during any temperature increaseand the length of any time at which the temperature is held constant.

In one embodiment, the metal hydroxide is heated at a rate oftemperature increase from 1° C./min to 50° C./min. In a preferredembodiment, the rate of temperature increase is from 3° C./min to 18°C./rain. In another preferred embodiment, the rate of temperatureincrease is 13° C./min.

In a preferred embodiment, the metal hydroxide is heated to atemperature from 500° C. to 620° C. In another preferred embodiment, thetemperature is from 500° C. to 600° C.

In one embodiment, the metal hydroxide is held at a constant temperatureabove the normal decomposition temperature for a period of time. In apreferred embodiment, the temperature is from 500° C. to 620° C. In apreferred embodiment, the temperature is from 500° C. to 600° C. Inanother preferred embodiment, the temperature is 520° C. In a preferredembodiment, the time is from 5 minutes to 300 minutes. In anotherpreferred embodiment, the time is from 5 minutes to 60 minutes. Inanother preferred embodiment, the time is from 10 minutes to 50 minutes.In another preferred embodiment, the time is from 20 minutes to 40minutes. In another preferred embodiment, the time is 23 minutes.

In one embodiment, the total time spent by the metal hydroxide at atemperature that is higher than the normal decomposition temperature forthe metal hydroxide is at least about 10 minutes.

Following heating of the metal hydroxide in the second gas streamcomprising CO₂, the metal hydroxide is dehydrated to regenerate themetal oxide.

In one embodiment, the metal hydroxide is heated to a temperature from500° C. to 800° C. to dehydrate the metal hydroxide and regenerate themetal oxide. In a preferred embodiment, the temperature is from 600° C.to 700° C.

Alternatively, the metal hydroxide may be dehydrated to regenerate themetal oxide by substituting the second gas stream comprising CO₂ with afourth gas stream in the first and second aspects. Similarly, in thethird aspect, the metal hydroxide is dehydrated to regenerate the metaloxide by substituting the second gas steam comprising CO₂ with a thirdgas stream.

In a preferred embodiment, the fourth gas stream of the first and secondaspects, and the third gas stream of the third aspect, has aconcentration of CO₂ such that the metal hydroxide dehydrates at thetemperature at which that gas stream substitutes for the second gasstream.

In another embodiment, the fourth gas stream of the first and secondaspects, and the third gas stream of the third aspect, does not includeCO₂ or comprises a low concentration of CO₂, for example ambient air.

In a preferred embodiment, the fourth gas stream of the first and secondaspects, and the third gas stream of the third aspect, comprises lessthan about 15% CO₂. In another embodiment, the gas stream comprises lessthan about 10% CO₂, less than about 5% CO₂, or less than about 2% CO₂,or less than about 1% CO₂.

The invention also contemplates embodiments in which the process ends atthis stage, to provide a metal oxide product having an enhancedresistance to attrition and fragmentation. The metal oxide product mayalso comprise some metal carbonate.

In one embodiment of the first and second aspects, the fourth gas streamis the same as the third gas stream in which the resulting metal oxideis then carbonated, as described below.

Alternatively, the metal hydroxide may be further heated in the secondgas stream comprising CO₂ until the dehydration temperature, which is afunction of the water vapor pressure and CO₂ concentration, is reached.

In the first and second aspects, the resulting metal oxide is thencarbonated in a third gas stream comprising CO₂ to regenerate the metalcarbonate. This carbonation reaction may be performed as describedabove.

The third gas stream of the first and second aspects may be a separategas stream that comprises CO₂. Alternatively, in one embodiment, thethird gas stream is the same as the first gas stream. In thisembodiment, the metal oxide captures further CO₂ from the first gasstream, which is then released as part of the first product gas streamwhen the cyclical process is repeated.

In another embodiment, the third gas stream of the first and secondaspects is the same as the second gas stream. In this embodiment, themetal hydroxide may be further heated in the second gas stream until itdehydrates. The temperature is then maintained or increased to carbonatethe metal oxide. In those embodiments wherein the second gas streamcomprises added CO₂, the metal oxide captures at least part of thisadded CO₂, which is then released as part of the first product gasstream when the cyclical process is repeated.

A preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream comprising    CO₂ to a temperature that is higher than the normal decomposition    temperature for the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate; and-   (i) repeating steps (a) to (h) using the metal carbonate regenerated    in step (h).

A further preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (h) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream comprising    CO₂ to a temperature that is higher than the normal decomposition    temperature for the metal hydroxide, and to a temperature and for a    time and at a concentration of CO₂ effective to suppress the    dehydration of the metal hydroxide and reduce the attrition and    fragmentation rates, compared to those that would otherwise occur,    of the metal oxide formed upon dehydration of the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate; and-   (i) repeating steps (a) to (h) using the metal carbonate regenerated    in step (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining CaCO₃ to generate CaO and produce a first product gas    stream comprising CO₂;-   (b) contacting the CaO with the first gas stream to carbonate the    CaO and regenerate the CaCO₃;-   (c) calcining the CaCO₃ regenerated in step (b) to regenerate the    CaO and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the CaO regenerated    in step (c);-   (e) contacting the CaO regenerated in step (c) with water to form    Ca(OH)₂;-   (f) heating the Ca(OH)₂ in a second gas stream comprising CO₂ to a    temperature that is higher than the normal decomposition temperature    for Ca(OH)₂;-   (g) dehydrating the Ca(OH)₂ to regenerate the CaO;-   (h) optionally repeating steps (e) to (g) using the CaO regenerated    in step (g);-   (i) contacting the CaO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the CaO and regenerate the CaCO₃;-   (j) optionally repeating steps (c) to (i) using the CaCO₃    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the CaCO₃ regenerated in step    (i).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining CaCO₃ to generate CaO and produce a first product gas    stream comprising CO₂;    -   (b) contacting the CaO with the first gas stream to carbonate        the CaO and regenerate the CaCO₃;-   (c) calcining the CaCO₃ regenerated in step (b) to regenerate the    CaO and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the CaO regenerated    in step (c);-   (e) contacting the CaO regenerated in step (c) with water to form    Ca(OH)₂;-   (f) heating the Ca(OH)₂ in a second gas stream comprising CO₂ to a    temperature that is higher than the normal decomposition temperature    for Ca(OH)₂, and to a temperature and for a time and at a    concentration of CO₂ effective to suppress the dehydration of the    Ca(OH)₂ and reduce the attrition and fragmentation rates, compared    to those that would otherwise occur, of the CaO formed upon    dehydration of the Ca(OH)₂;-   (g) dehydrating the Ca(OH)₂ to regenerate the CaO;-   (h) optionally repeating steps (e) to (g) using the CaO regenerated    in step (g);-   (i) contacting the CaO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the CaO and regenerate the CaCO₃;-   (j) optionally repeating steps (c) to (i) using the CaCO₃    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the CaCO₃ regenerated in step    (i).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a mixture of CaCO₃ and MgCO₃ to generate a mixture of    CaO and MgO and produce a first product gas stream comprising CO₂;-   (b) contacting the mixture of CaO and MgO with the first gas stream    to carbonate mixture of CaO and MgO and regenerate the mixture of    CaCO₃ and MgCO₃;-   (c) calcining the mixture of CaCO₃ and MgCO₃ regenerated in step (b)    to regenerate the mixture of CaO and MgO and produce a second    product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the mixture of CaO    and MgO regenerated in step (c);-   (e) contacting the mixture of CaO and MgO regenerated in step (c)    with water to form a mixture of Ca(OH)₂ and Mg(OH)₂;-   (f) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a second gas    stream comprising CO₂ to a temperature that is higher than the    normal decomposition temperature for the mixture of Ca(OH)₂ and    Mg(OH)₂;-   (g) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO;-   (h) optionally repeating steps (e) to (g) using the mixture of CaO    and MgO regenerated in step (g);-   (i) contacting the mixture of CaO and MgO regenerated in step (g)    with a third gas stream comprising CO₂ to carbonate the mixture of    CaO and MgO and regenerate the mixture of CaCO₃ and MgCO₃;-   (j) optionally repeating steps (c) to (i) using the mixture of CaCO₃    and MgCO₃ regenerated in step (i); and-   (k) repeating steps (a) to (j) using the mixture of CaCO₃ and MgCO₃    regenerated in step (i).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a mixture of CaCO₃ and MgCO₃ to generate a mixture of    CaO and MgO and produce a first product gas stream comprising CO₂;-   (b) contacting the mixture of CaO and MgO with the first gas stream    to carbonate the mixture of CaO and MgO and regenerate the mixture    of CaCO₃ and MgCO₃;-   (c) calcining the mixture of CaCO₃ and MgCO₃ regenerated in step (b)    to regenerate the mixture of CaO and MgO and produce a second    product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the mixture of CaO    and MgO regenerated in step (c);-   (e) contacting the mixture of CaO and MgO regenerated in step (c)    with water to form a mixture of Ca(OH)₂ and Mg(OH)₂;-   (f) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a second gas    stream comprising CO₂ to a temperature that is higher than the    normal decomposition temperature for the mixture of Ca(OH)₂ and    Mg(OH)₂, and to a temperature and for a time and at a concentration    of CO₂ effective to suppress the dehydration of the mixture of    Ca(OH)₂ and Mg(OH)₂ and reduce the attrition and fragmentation    rates, compared to those that would otherwise occur, of the mixture    of CaO and MgO formed upon dehydration of the mixture of Ca(OH)₂ and    Mg(OH)₂;-   (g) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO;-   (h) optionally repeating steps (e) to (g) using the mixture of CaO    and MgO regenerated in step (g);-   (i) contacting the mixture of CaO and MgO regenerated in step (g)    with a third gas stream comprising CO₂ to carbonate the mixture of    CaO and MgO and regenerate the mixture of CaCO₃ and MgCO₃;-   (j) optionally repeating steps (c) to (i) using the mixture of CaCO₃    and MgCO₃ regenerated in step (i); and-   (k) repeating steps (a) to (j) using the mixture of CaCO₃ and MgCO₃    regenerated in step (i).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining CaCO₃ to generate CaO and produce a first product gas    stream comprising CO₂;-   (b) contacting the CaO with the first gas stream to carbonate the    CaO and regenerate the CaCO₃;-   (c) calcining the CaCO₃ regenerated in step (b) to regenerate the    CaO and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the CaO regenerated    in step (c);-   contacting the CaO regenerated in step (c) with water to form    Ca(OH)₂;-   (f) heating the Ca(OH)₂ in a second gas stream comprising CO₂ to a    temperature that is higher than the normal decomposition temperature    for Ca(OH)₂;-   (g) dehydrating the Ca(OH)₂ to regenerate the CaO;-   (h) contacting the CaO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the CaO and regenerate the CaCO₃;-   (i) repeating steps (a) to (h) using the CaCO₃ regenerated in step    (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining CaCO₃ to generate CaO and produce a first product gas    stream comprising CO₂;-   (b) contacting the CaO with the first gas stream to carbonate the    CaO and regenerate the CaCO₃;-   (c) calcining the CaCO₃ regenerated in step (b) to regenerate the    CaO and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the CaO regenerated    in step (c);-   (e) contacting the CaO regenerated in step (c) with water to form    Ca(OH)₂;-   (f) heating the Ca(OH)₂ in a second gas stream comprising CO₂ to a    temperature that is higher than the normal decomposition temperature    for Ca(OH)₂, and to a temperature and for a time and at a    concentration of CO₂ effective to suppress the dehydration of the    Ca(OH)₂ and reduce the attrition and fragmentation rates, compared    to those that would otherwise occur, of the CaO formed upon    dehydration of the Ca(OH)₂;-   (g) dehydrating the Ca(OH)₂ to regenerate the CaO;-   (h) contacting the CaO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the CaO and regenerate the CaCO₃;-   (i) repeating steps (a) to (h) using the CaCO₃ regenerated in step    (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining CaCO₃ to generate CaO and produce a first product gas    stream comprising CO₂;-   (b) contacting the CaO with the first gas stream to carbonate the    CaO and regenerate the CaCO₃;-   (c) calcining the CaCO₃ regenerated in step (b) to regenerate the    CaO and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the CaO regenerated    in step (c);-   (e) contacting the CaO regenerated in step (c) with water vapor at    an absolute humidity from 5% to 100% and at a temperature from    100° C. to 700° C. to form Ca(OH)₂;-   (f) heating the Ca(OH)₂ in a second gas stream comprising from 20%    to 100% CO₂ to a temperature from 500° C. to 620° C.;-   (g) dehydrating the Ca(OH)₂ to regenerate the CaO by heating the    Ca(OH)₂ to a temperature from 600° C. to 700° C.;-   (h) contacting the CaO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the CaO and regenerate the CaCO₃;-   (i) repeating steps (a) to (h) using the CaCO₃ regenerated in step    (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of

-   (a) calcining CaCO₃ to generate CaO and produce a first product gas    stream comprising CO₂;-   (b) contacting the CaO with the first gas stream to carbonate the    CaO and regenerate the CaCO₃;-   calcining the CaCO₃ regenerated in step (b) to regenerate the CaO    and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the CaO regenerated    in step (c);-   (e) contacting the CaO regenerated in step (c) with water vapor at    an absolute humidity from 5% to 100% and at a temperature from    100° C. to 700° C. to form Ca(OH)₂;-   (f) heating the Ca(OH)₂ in a second gas stream comprising from 20%    to 100% CO₂ to a temperature from 500° C. to 600° C.;-   (g) dehydrating the Ca(OH)₂ to regenerate the CaO in a gas stream    comprising less than about 15% CO₂;-   (h) contacting the CaO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the CaO and regenerate the CaCO₃;-   (i) repeating steps (a) to (h) using the CaCO₃ regenerated in step    (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining MgCO₃ to generate MgO and produce a first product gas    stream comprising CO₂;-   (b) contacting the MgO with the first gas stream to carbonate the    MgO and regenerate the MgCO₃;-   (c) calcining the MgCO₃ regenerated in step (b) to regenerate the    MgO and produce a second product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the MgO regenerated    in step (c);

(e) contacting the MgO regenerated in step (c) with water to formMg(OH)₂;

-   (f) heating the Mg(OH)₂ in a second gas stream comprising CO₂ to a    temperature that is higher than the normal decomposition temperature    for Mg(OH)₂;-   (g) dehydrating the Mg(OH)₂ to regenerate the MgO;-   (h) contacting the MgO regenerated in step (g) with a third gas    stream comprising CO₂ to carbonate the MgO and regenerate the MgCO₃;-   (i) repeating steps (a) to (h) using the MgCO₃ regenerated in step    (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a mixture of CaCO₃ and MgCO₃ to generate a mixture of    CaO and MgO and produce a first product gas stream comprising CO₂;-   (b) contacting a mixture of CaO and MgO with the first gas stream to    carbonate the mixture of CaO and MgO and regenerate the mixture of    CaCO₃ and MgCO₃;-   (c) calcining the mixture of CaCO₃ and MgCO₃ regenerated in step (b)    to regenerate the mixture of CaO and MgO and produce a second    product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the mixture of CaO    and MgO regenerated in step (c);-   (e) contacting a mixture of CaO and MgO regenerated in step (c) with    water to form a mixture of Ca(OH)₂ and Mg(OH)₂;-   (t) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a second gas    stream comprising CO₂ to a temperature that is higher than the    normal decomposition temperature for the mixture of Ca(OH)₂ and    Mg(OH)₂;-   (g) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO;-   (h) contacting the mixture of CaO and MgO regenerated in step (g)    with a third gas stream comprising CO₂ to carbonate the mixture of    CaO and MgO and regenerate the mixture of CaCO₃ and MgCO₃;-   (i) repeating steps (a) to (h) using the mixture of CaCO₃ and MgCO₃    regenerated in step (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a mixture of CaCO₃ and MgCO₃ to generate a mixture of    CaO and MgO and produce a first product gas stream comprising CO₂;-   (b) contacting a mixture of CaO and MgO with the first gas stream to    carbonate the mixture of CaO and MgO and regenerate the mixture of    CaCO₃ and MgCO₃;-   (c) calcining the mixture of CaCO₃ and MgCO₃ regenerated in step (b)    to regenerate the mixture of CaO and MgO and produce a second    product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the mixture of CaO    and MgO regenerated in step (c);-   (e) contacting a mixture of CaO and MgO regenerated in step (c) with    water to form a mixture of Ca(OH)₂ and Mg(OH)₂;-   (f) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a second gas    stream comprising CO₂ to a temperature that is higher than the    normal decomposition temperature for the mixture of Ca(OH)₂ and    Mg(OH)₂, and to a temperature and for a time and at a concentration    of CO₂ effective to suppress the dehydration of the mixture of    Ca(OH)₂ and Mg(OH)₂ and reduce the attrition and fragmentation    rates, compared to those that would otherwise occur, of the mixture    of CaO and MgO formed upon dehydration of the mixture of Ca(OH)₂ and    Mg(OH)₂;-   (g) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO;-   (h) contacting the mixture of CaO and MgO regenerated in step (g)    with a third gas strewn comprising CO₂ to carbonate the mixture of    CaO and MgO and regenerate the mixture of CaCO₃ and MgCO₃;-   (i) repeating steps (a) to (h) using the mixture of CaCO₃ and MgCO₃    regenerated in step (h).

Another preferred embodiment of the invention comprises a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a mixture of CaCO₃ and MgCO₃ to generate a mixture of    CaO and MgO and produce a first product gas stream comprising CO₂;-   contacting the mixture of CaO and MgO with the first gas stream to    carbonate the mixture of CaO and MgO and regenerate the mixture of    CaCO₃ and MgCO₃;-   (c) calcining the mixture of CaCO₃ and MgCO₃ regenerated in step (b)    to regenerate the mixture of CaO and MgO and produce a second    product gas stream comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the mixture of CaO    and MgO regenerated in step (c);-   (e) contacting the mixture of CaO and MgO regenerated in step (c)    with water vapor at an absolute humidity from 5% to 100% and at a    temperature from 100° C. to 700° C. to forms a mixture of Ca(OH)₂    and Mg(OH)₂;-   (f) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a second gas    stream comprising from 20% to 100% CO₂ to a temperature from 500° C.    to 620° C.;-   (g) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO by heating the mixture of Ca(OH)₂ and Mg(OH)₂    to a temperature from 600° C. to 700° C.;-   (h) contacting the mixture of CaO and MgO regenerated in step (g)    with a third gas stream comprising CO₂ to carbonate the mixture of    CaO and MgO and regenerate the mixture of CaCO₃ and MgCO₃;-   (i) repeating steps (a) to (h) using the mixture of CaCO₃ and MgCO₃    regenerated in step (h).

The mechanism of decomposition of Ca(OH)₂ is thought to proceed viaseveral steps (O. Chaix-Pluchery et al, J. Solid State Chem, 50 (1983)247-255), Initially, as the Ca(OH)₂ is heated below the normaldecomposition temperature, hydrogen atoms detach to form mobile protonswhich then attach to hydroxide ions to form water molecules. As thetemperature is further increased these water molecules aggregate intowater rich zones and eventually escape from the crystal via channels orpathways in the crystal lattice. In the presence of proton donormolecules, such as chemisorbed water, the normal decompositiontemperature can be elevated by many tens of degrees.

Chemisorbed water may be formed in the presence of CO₂ gas during thedehydration of the Ca(OH)₂, which may result in the significantelevation of the decomposition temperature observed in the Examples.

The present applicants have determined that, in the presence of a gaseffective to suppress the dehydration of the metal hydroxide, thetemperature at which the metal hydroxide dehydrates is elevated withrespect to the dehydration temperature in the absence of the gas.

Accordingly, the invention contemplates alternative embodiments in whichthe metal hydroxide is subjected to dehydration at an elevatedtemperature by heating in an atmosphere comprising an acidic gas, whichacts as a proton donor or induces the formation of proton donors. Insuch an atmosphere, the metal hydroxide may be heated to a temperatureabove that at which it normally dehydrates.

In one embodiment, the acidic gas comprises a gas selected from thegroup consisting of: H₂O; CO₂; SO₂; SO_(x); NO₂; and NO_(x); andmixtures of any two or more thereof. The acid gas may be a mixture of anacid gas together with other, non-acid gases.

In one embodiment, the heating of Ca(OH)₂ in the presence of an acidgas, which is in contact with the Ca(OH)₂ from temperatures well belowthe normal dehydration temperature of 445° C., results in an increase inthe dehydration temperature and reduced attrition and fragmentation in afluidized bed reactor.

Accordingly, in a fourth aspect, the present invention provides aprocess for separating CO₂ from a first gas stream comprising CO₂, theprocess comprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream, wherein the    second gas stream comprises a gas effective to suppress the    dehydration of the metal hydroxide, to a temperature that is higher    than the normal decomposition temperature for the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In a fifth aspect, the present invention provides a process forseparating CO₂ from a first gas stream comprising CO₂, the processcomprising the steps of:

-   (a) calcining a metal carbonate to generate a metal oxide and    produce a first product gas stream comprising CO₂;-   (b) contacting the metal oxide with the first gas stream to    carbonate the metal oxide and regenerate the metal carbonate;-   (c) calcining the metal carbonate regenerated in step (b) to    regenerate the metal oxide and produce a second product gas stream    comprising CO₂;-   (d) optionally repeating steps (b) and (c) using the metal oxide    regenerated in step (c);-   (e) contacting the metal oxide regenerated in step (c) with water to    form a metal hydroxide;-   (f) heating the metal hydroxide in a second gas stream, wherein the    second gas stream comprises a gas effective to suppress the    dehydration of the metal hydroxide, to a temperature that is higher    than the normal decomposition temperature for the metal hydroxide,    and to a temperature and for a time and at a concentration of the    gas effective to suppress the dehydration of the metal hydroxide and    reduce the attrition and fragmentation rates, compared to those that    would otherwise occur, of the metal oxide formed upon dehydration of    the metal hydroxide;-   (g) dehydrating the metal hydroxide to regenerate the metal oxide;-   (h) optionally repeating steps (e) to (g) using the metal oxide    regenerated in step (g);-   (i) contacting the metal oxide regenerated in step (g) with a third    gas stream comprising CO₂ to carbonate the metal oxide and    regenerate the metal carbonate;-   (j) optionally repeating steps (c) to (i) using the metal carbonate    regenerated in step (i); and-   (k) repeating steps (a) to (j) using the metal carbonate regenerated    in step (i).

In a sixth aspect, the present invention provides a process forproducing a metal oxide by dehydrating a metal hydroxide, the processcomprising heating the metal hydroxide in a gas stream, wherein the gasstream comprises a gas effective to suppress the dehydration of themetal hydroxide, to a temperature higher than the normal dehydrationtemperature for the metal hydroxide, and dehydrating the metal hydroxideto obtain the metal oxide.

In a seventh aspect, the present invention provides a process forrestoring the ability of a metal oxide to react with CO₂, wherein themetal oxide is used in a cyclic process, wherein the metal oxide isreacted with CO₂ to form a metal carbonate and the metal carbonate iscalcined to regenerate the metal oxide, the process comprising the stepsof

-   (a) contacting the metal oxide with water to form a metal hydroxide;-   (b) heating the metal hydroxide in a gas stream, wherein the gas    stream comprises a gas effective to suppress the dehydration of the    metal hydroxide, to a temperature higher than the normal dehydration    temperature for the metal hydroxide; and-   (c) dehydrating the metal hydroxide to regenerate the metal oxide.

In a preferred embodiment, the gas effective to suppress the dehydrationof the metal hydroxide is an acidic gas. In one embodiment, the acidicgas comprises a gas selected from the group consisting of: H₂O; CO₂;SO₂; SO_(x); NO₂; and NO_(x); and mixtures of any two or more thereof.

In a preferred embodiment, the acidic gas is CO₂.

Other preferred embodiments of the fourth to seventh aspects of theinvention incorporate features of the various embodiments of the firstto third aspects of the invention described above.

A preferred embodiment of the present invention comprises a process forproducing CaO by dehydrating Ca(OH)₂, the process comprising heatingCa(OH)₂ in a gas stream comprising CO₂ to a temperature higher than thenormal dehydration temperature of Ca(OH)₂, and dehydrating the Ca(OH)₂to obtain CaO.

A further preferred embodiment of the present invention comprises aprocess for producing MgO by dehydrating Mg(OH)₂, the process comprisingheating Mg(OH)₂ in a gas stream comprising CO₂ to a temperature higherthan the normal dehydration temperature of Mg(OH)₂, and dehydrating theMg(OH)₂ to obtain MgO.

Another preferred embodiment of the present invention comprises aprocess for producing a mixture of CaO and MgO by dehydrating a mixtureof Ca(OH)₂ and Mg(OH)₂, the process comprising heating a mixture ofCa(OH)₂ and Mg(OH)₂ in a gas stream comprising CO₂ to a temperaturehigher than the normal dehydration temperature of the mixture of Ca(OH)₂and Mg(OH)₂, and dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ toobtain a mixture of CaO and MgO.

Another preferred embodiment of the present invention comprises aprocess for producing CaO by dehydrating Ca(OH)₂, the process comprisingheating Ca(OH)₂ in a gas stream comprising 20% to 100% CO₂ to atemperature from 500° C. to 620° C., and dehydrating the Ca(OH)₂ toobtain CaO.

Another preferred embodiment of the present invention comprises aprocess for producing a mixture of CaO and MgO by dehydrating a mixtureof Ca(OH)₂ and Mg(OH)₂, the process comprising heating a mixture ofCa(OH)₂ and Mg(OH)₂ in a gas stream comprising 20% to 100% CO₂ to atemperature from 500° C. to 620° C., and dehydrating the mixture ofCa(OH)₂ and Mg(OH)₂ to obtain a mixture of CaO and MgO.

Another preferred embodiment of the present invention comprises aprocess for restoring the ability of CaO to absorb, CO₂, wherein the CaOis used in a cyclic process, wherein the CaO is reacted with CO₂ to formCaCO₃ and CaCO₃ is calcined to regenerate CaO, the process comprisingthe steps of:

-   (a) contacting CaO with water to form Ca(OH)₂;-   (b) heating the Ca(OH)₂ in a gas stream comprising CO₂ to a    temperature higher than the normal dehydration temperature of    Ca(OH)₂; and-   (c) dehydrating the Ca(OH)₂ to regenerate the CaO.

Another preferred embodiment of the present invention comprises aprocess for restoring the ability of MgO to absorb CO₂, wherein the MgOis used in a cyclic process, wherein the MgO is reacted with CO₂ to formMgCO₃ and MgCO₃ is calcined to regenerate MgO, the process comprisingthe steps of:

-   (a) contacting MgO with water to form Mg(OH)₂;-   (b) heating the Mg(OH)₂ in a gas stream comprising CO₂ to a    temperature higher than the normal dehydration temperature of    Mg(OH)₂; and-   (c) dehydrating the Mg(OH)₂ to regenerate the MgO.

Another preferred embodiment of the present invention comprises aprocess for restoring the ability of a mixture of CaO and MgO to absorbCO₂, wherein the mixture of CaO and MgO is used in a cyclic process,wherein the mixture of CaO and MgO is reacted with CO₂ to form a mixtureof CaCO₃ and MgCO₃ and the mixture of CaCO₃ and MgCO₃ is calcined toregenerate the mixture of CaO and MgO, the process comprising the stepsof:

-   (a) contacting a mixture of CaO and MgO with water to form a mixture    of Ca(OH)₂ and Mg(OH)₂;-   (b) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a gas stream    comprising CO₂ to a temperature CO₂ to a temperature higher than the    normal dehydration temperature of the mixture of Ca(OH)₂ and Mg(OH)₂    in the absence of CO₂; and-   (c) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO.

Another preferred embodiment of the present invention comprises aprocess for restoring the ability of a CaO to absorb CO₂, wherein theCaO is used in a cyclic process, wherein the CaO is reacted with CO₂ toform CaCO₃ and CaCO₃ is calcined to regenerate CaO, the processcomprising the steps of:

-   (a) contacting CaO with water to form Ca(OH)₂;-   (b) heating the Ca(OH)₂ in a gas stream comprising 20% to 100% CO₂    to a temperature from 500° C. to 620° C.; and-   (c) dehydrating the Ca(OH)₂ to regenerate the CaO.

Another preferred embodiment of the present invention comprises aprocess for restoring the ability of a mixture of CaO and MgO to absorbCO₂, wherein the mixture of CaO and MgO is used in a cyclic process,wherein the mixture of CaO and MgO is reacted with CO₂ to form a mixtureof CaCO₃ and MgCO₃ and the mixture of CaCO₃ and MgCO₃ is calcined toregenerate the mixture of CaO and MgO, the process comprising the stepsof:

-   (a) contacting a mixture of CaO and MgO with water to form a mixture    of Ca(OH)₂ and Mg(OH)₂;-   (b) heating the mixture of Ca(OH)₂ and Mg(OH)₂ in a gas stream    comprising 20% to 100% CO₂ to a temperature from 500° C. to 620° C.;    and-   (c) dehydrating the mixture of Ca(OH)₂ and Mg(OH)₂ to regenerate the    mixture of CaO and MgO.

In another aspect, the present invention provides apparatus adapted toperform the process of the invention.

The following non-limiting examples are provided to illustrate thepresent invention and in no way limit the scope thereof.

EXAMPLES

Some of the experiments described below were carried out in a fluidizedbed reactor with a bed volume of 1.2 liters and diameter of 8.1 cm.Gases of controlled composition and flow rate were supplied to thebottom of the temperature controlled fluidized bed reactor. Thetemperature of the fluidized bed was monitored, and the flow rates ofthe emitted gases were measured with mass flow meters. The elutriatedsolids were separated from the gas flow in a cyclone. Water output fromthe reactor was condensed in a water trap. A schematic diagram of thefluidized bed reactor is shown in FIG. 1.

Other experiments were performed in using an experimental setupidentical to that shown in FIG. 1, but using a smaller reactor. Theseexperiments have the prefix P. The diameter of the reactor used forthese experiments was 32 mm and the bed volume was about 0.13 liters.Unless otherwise specified, all of the gas proportions were keptconstant compared to the experiments in the larger reactor. The reactiontimes for the experiments in the small reactor were typically shorterthat those in the large reactor because of the reduced bed volume.

Limestone was supplied by Taylors Lime, Makareao, Otago, New Zealand.The limestone was sieved, washed and then sieved between 300-600 μm.

A typical experiment consisted of repeated reaction cycles. Eachreaction cycle started with CaO which was first hydrated, thendehydrated, then carbonated and finally calcined so that the resultingsolid was also CaO. The hydration of the CaO was carried out with aflowing mixture of water vapor (about 20%) and N₂ at 400° C. Unlessotherwise specified, dehydration under fluidized bed conditions wascarried out in a flow of N₂ at 450-650° C. Carbonation was performed ina flow of CO₂ (20%) and N₂ at 650° C. in the large reactor and, unlessotherwise specified, in a flow of CO₂ (37.5%) in N₂ at 620° C. in thesmall reactor. Calcination was performed in flowing N₂ under reducedpressure at 805° C.

At the end of the reaction cycle, the solid was discharged and sieved,and the fines (<150 μm) removed from the bulk of the solid and putaside. The fines that had elutriated were recovered from the cyclone andthe pipe leading to it.

Initial Experiment

The initial experiment involved cycling a CaO sorbent in a fluidized bedthrough successive calcination-hydration-dehydration-carbonationreaction cycles and measuring the rates, the extent of the reactions,and the degree of fragmentation during the cycling. A sample was takenat the completion of every reaction cycle and examined for particle sizedistribution. The reaction cycling regime is shown in FIG. 2.

An experiment (Cycle 4) comprising five reaction cycles was conducted.The sample was calcined at 805° C. and at reduced pressure. Thetemperature profile as a function of time for Cycle 4 is shown in FIG.3.

Results and Discussion Fragmentation Results

The cycled sorbent was sieved and separated into three categories:

-   -   150-300 μm: these were not initially present in the sorbent and        are, therefore, the product of fragmentation;    -   less than 150 μm: fines that remain within the bed throughout        the reaction cycles; and    -   elutriated particles: particles collected in the cyclone after        each reaction cycle.

Table 1 illustrates the generation of fines under Cycle 4 reactionconditions expressed as cumulative percentages.

The amount of fines produced during each reaction cycle increased withtime. The amount of elutriated particles (captured in the cyclone)remained reasonably constant for each reaction cycle under Cycle 4reaction conditions, while the fines produced that stay in the bulkincreased with time.

TABLE 1 Fines accumulation under Cycle 4 reaction conditions. CumulativePercentages Calcination 150-300 <150 Cyclone Total Fines 1 1.3 0.4 0.50.9 +0.8 +0.5 +1.3 2 2.6 1.2 1.0 2.2 +0.7 +0.6 +1.3 3 4.0 1.9 1.6 3.5+0.8 +0.5 +1.3 4 4.8 2.7 2.1 4.8 +0.9 +0.6 +1.5 5 6.4 3.6 2.7 6.3 +1.1+0.8 +1.9 6 7.6 4.7 3.5 8.2 Final 7.6 5.2 3.5 8.7

The rate of fragmentation based on the amount of sorbent lost to finesimplies a lifetime of 40-50 cycles for the sorbent under Cycle 4reaction conditions. The data in Table 1 show that the hydration stepresults in substantial fragmentation of the sorbent.

Reaction Conversions Hydration

The total amount of water captured by the sorbent was dete/imined fromthe amount of water released during dehydration and captured in thewater trap; however this is a fairly imprecise method. The length of therun was determined by the variation of measured water vapor pressurewith time.

Carbonation

The amount of CO₂ actually released was determined from the mass flowmeters and calibrated by assuming that the first calcinationcorresponded to a 100% release of CO₂ because the initial sample wascompletely carbonated.

Table 2 shows the extent of CO₂ release for each cycle and the extent ofhydration on the preceding cycle.

TABLE 2 CO₂ capture under Cycle 4 reaction conditions. Calcination % CO₂Capture % Previous Hydration 1 100 Nil 2 89 >55 3 70 76 4 80 67 5 73 596 68 60

Further Fragmentation Experiments and Intermittent Hydration

Results from the experiments under Cycle 4 reaction conditions showedthat a hydration step in every cycle reduced the cycling life of thesorbent by expansion, vesiculation and weakening of the sorbentparticles, inducing fragmentation.

A further experiment was conducted that involved cycling a lime sorbentin a fluidized bed through successivecalcination-hydration-dehydration-carbonation cycles. However, in thisexperiment (Cycle 5), the hydration was on an intermittent basis. Ahydration/dehydration was performed on every thirdcarbonation/calcination cycle. The reaction cycling regime is shown inFIG. 4.

The temperature profile as a function of time is shown in FIG. 5 forthose carbonation/calcination cycles in which there was not a hydrationstep. For those carbonation/calcination cycles in which there was ahydration step, the temperature profile as a function of time was thatshown in FIG. 3. So the overall sequence for Cycle 5 was twocarbonation-calcination reaction cycles according to the temperatureprofile shown in FIG. 5, followed by onehydration-dehydration-carbonation-calcination reaction cycle accordingto the temperature profile shown in FIG. 3 and so on.

Table 3 illustrates the generation of fines under Cycle 5 reactionconditions expressed as cumulative percentages.

TABLE 3 Fines accumulation under Cycle 5 reaction conditions. CumulativePercentages 150-300 <150 Cyclone Total Fines Calcination 2 2.7 0.5 0.81.2 4 6.0 0.7 1.0 1.7 Hydration 5 4.4 1.1 1.5 2.6 7 4.8 1.5 1.6 3.1Hydration 8 7.1 2.3 2.6 4.9 10  7.6 3.3 3.0 6.3 Final 7.6 3.3 3.0 6.3

Reaction conversions under Cycle 5 reaction conditions are shown inTable 4.

TABLE 4 CO₂ capture under Cycle 5 reaction conditions. Calcination % CO₂Capture % Previous Hydration 1 100 2 79 0 3 >50 0 4 58 0 5 65 67 6 52 07 48 0 8 63 71 9 >30 — 10 39 —

Discussion

The data in Table 3 show that most of fines are created during thehydration/dehydration steps, which is consistent with the experimentsusing the Cycle 4 reaction conditions.

The intermittent hydration utilized under Cycle 5 reaction conditionsprovided good results, in which an average sorhent activity of 61% wasmaintained over 9 carbonation/calcination cycles, while only 6.3% of thematerial was lost to fines. This was a significant improvement over theCycle 4 reactions conditions, which included a hydration step in everycycle. While the Cycle 4 reaction conditions retained a higher sorbentactivity of around 70%, 83% of the sorbent material was lost to finesafter five reaction cycles.

These results demonstrate that intermittent hydration results in aminimal loss of sorbent activity and a considerable reduction infragmentation rates compared to periodic hydration. The rate offragmentation based on the amount of sorbent lost to fines implies alifetime of 130 cycles for the sorbent under Cycle 5 reactionconditions.

Further Experiments on Different Limestone Materials

The experiments under Cycle 4 and Cycle 5 reaction conditions describedabove were repeated on sorbent material from a different part of theTaylors Lime quay. These experiments were designated Cycle 8 and Cycle7. These experiments demonstrated the general applicability of thereaction conditions described above in reducing fragmentation of thesorbent while also maintaining high levels of CO₂ absorption activity.

The Cycle 7 experiment subjected limestone material to the sameintermittent hydration conditions as Cycle 5. The fragmentation resultsare shown in Table 5 and the reaction conversions in Table 6.

TABLE 5 Fines accumulation under Cycle 7 reaction conditions. CumulativePercentages Calcination 150-300 <150 Cyclone Total Fines 2 3.0 1.3 0.61.9 4 4.3 1.8 1.0 2.8 Hydration 5 5.7 2.3 2.0 4.3 Final 5.7 2.3 2.0 4.3

TABLE 6 CO₂ capture under Cycle 7 reaction conditions. Carbonation % CO₂Capture 1 100 2 76 3 70 4 68

The Cycle 8 experiment subjected the limestone to the same periodichydration conditions as Cycle 4, in which there was a hydration stepafter every calcination. The final reaction cycle of this experimentincluded a modified dehydration step in which the Ca(OH)₂ was dehydratedin a stream of CO₂ (20%) and N₂. The same temperature profile shown inFIG. 3 was used for the modified dehydration step, but the flow of CO₂was started at minute 87 and maintained through to minute 206. Thismodification of the reaction conditions reduced the fragmentationlevels.

Table 7 illustrates the generation of fines for Cycle 8 reactionconditions expressed as cumulative percentages. D/K signifies themodified dehydration step.

TABLE 7 Fines accumulation under Cycle 7 reaction conditions. CumulativePercentages Cycle 150-300 <150 Cyclone Total Fines 1 2.3 1.0 1.3 2.3 24.2 2.4 2.2 4.6 3 5.9 3.7 4.0 7.7 4 7.5 5.0 5.1 10.1 D/K 5 8.5 5.9 5.911.8 Final 8.5 6.4 5.9 12.3

Reaction conversions under Cycle 8 reaction conditions are shown inTable 8.

TABLE 8 CO₂ capture under Cycle 8 reaction conditions. Calcination % CO₂Capture % Previous Hydration 1 100 0 2 77 56 3 63 68 4 77 66 5 51 59

Discussion

Table 9 and FIG. 6 compare the fragmentation results, as shown in Tables1 and 3, for Cycle 4 reaction conditions (periodic hydration—hydrationafter every calcination) and Cycle 5 reaction conditions (intermittenthydration—hydration after every three carbonation-calcination reactioncycles). The sorbent materials used for the experiments under Cycle 4and Cycle 5 reaction conditions were sourced from the same part of thequarry. Also compared are the fragmentation results, as shown in Tables7 and 5, for Cycle 8 reaction conditions (periodic hydration—hydrationafter every calcination) and Cycle 7 reaction conditions (intermittenthydration—hydration after every three carbonation-calcination reactioncycles). The sorbent materials used for the experiments under Cycle 8and Cycle 7 reaction conditions were sourced from the same part of thequarry.

Table 9 shows the normalized amount of fines at different points of thereaction cycles expressed as cumulative percentages.

TABLE 9 Fines accumulation under Cycle 4, 5, 7 and 8 reactionconditions. Cycle 4 Cycle5 Cycle 8 Cycle 7 Calcination PeriodicIntermittent Periodic Intermittent 1 0.9% 2.3% 2 2.2% 1.2% 4.6% 1.9% 33.5% 7.7% 4 4.8% 1.7% 10.1% 2.8% 5 6.3% 2.6% 11.8% 4.3% Ratio 4/5 2.468/7 2.75

The fragmentation results show that reaction conditions utilizingintermittent hydration result in reduced fragmentation levels for bothlimestones when compared to reaction conditions utilizing periodichydration.

Table 10 shows the reaction conversions under the different reactionconditions for the different sorbents,

TABLE 10 CO₂ capture under Cycle 4, 5, 7 and 8 reaction conditions.Calcination Cycle 4 Cycle 8 Cycle 5 Cycle 7 1 84% 88% 92% 100% 2 74% 76%76% 76% 3 70% 74% 64% 70%

The Modified Dehydration Step

The following experiments utilized the modified dehydration step thatwas used in the final cycle under Cycle 8 reaction conditions. In thisstep, 20% CO₂ was added to the N₂ present during the dehydration. Theconditions are otherwise identical to the dehydration conditionsutilized above. The reaction cycling regime is shown in FIG. 7.

Two experiments investigated the effects of the modified dehydrationstep in the small fluidized bed reactor described above. The experimentswere conducted for 22 calcinations. In one experiment (Cycle P1), thereaction conditions were identical to Cycle 5 and used the same materialin a reaction sequence including intermittent hydration (hydration everythree calcinations). The other experiment (Cycle P2) used the samematerial in a reaction sequence including intermittent hydration (everythree calcinations) but the hydration was followed by a modifieddehydration step, instead of the conventional dehydration step used inCycle P1.

The reaction times for Cycles P1 and P2 were shorter than those forCycle 5 because of the reduced bed volume in the small reactor and were:

-   -   calcination: 36 minutes    -   carbonation: 23 minutes    -   hydration: 40 minutes    -   dehydration: 22 minutes

Table 11 illustrates the production of fines, in weight, and ascumulative percentages at every cycle under Cycle P1 and Cycle P2reaction conditions.

TABLE 11 Fines accumulation under Cycle P1 and Cycle P2 reactionconditions. Cumulative mass (g) Cumulative percentages Calcination CycleP1 Cycle P2 Cycle P1 Cycle P2 2 1.79 1.88 3.2 3.4 5 3.64 1.81 6.5 3.2 84.17 1.6 7.4 2.9 10 4.2 1.53 7.5 2.7 22 6.63 1.85 11.8 3.3

The data in Table 11 show that the modified dehydration step (Cycle P2)significantly reduced the amount of fines produced during the reactioncycling.

The reaction conversions under Cycle P1 and Cycle P2 reaction conditionsare shown in FIG. 8. The measurements over 100% are obviously incorrectand are due to water residues in the system, which increase the massflow meter measurements.

Both the Cycle P1 and Cycle P2 reaction conditions achieve very similarCO₂ capture capacities, which are significantly higher than those forconventional carbonation-calcination cycling.

Four more experiments were conducted in the small fluidized bed reactorwith conditions identical to those of the large reactor. Theseexperiments included the use of different sorbent materials andincreased the number of reaction cycles beyond the 22 calcinations forCycles P1 and P2.

The reaction conditions for Cycle P5 were identical to those for CycleP2 but used sorbent material from a different part of the Taylors Limequarry in a reaction sequence including intermittent hydration (everythree calcinations) but in which the hydration was followed by themodified dehydration step. The reaction conditions for Cycle P3 wereidentical to those for Cycle P1, but used a different sorbent materialin a reaction sequence including intermittent hydration (hydration everythree carbonations). The reaction conditions for Cycle P4 were identicalto those for Cycle 4 and used the same material in a reaction sequencethat used periodic hydration. The reaction conditions for Cycle P9 wereidentical to those for Cycle P2 but used a different sorbent material ina reaction sequence including intermittent hydration (every threecalcinations) but in which the hydration was followed by the modifieddehydration step.

The sorbent material for Cycle P3 was Fernbrae dolomitic lime suppliedby Golden Bay Cement, Portland, Northland, New Zealand. The sorbentmaterial for Cycle P9 was OmyaCal limestone supplied by Omya. NewZealand Limited, Te Kuiti, Waikato, New Zealand. The sorbent materialwas sieved, washed and then sieved between 300-600 μm.

Table 12 illustrates the production of fines with a particle size ofless than 150 μm as cumulative percentages and the average reactionconversions under Cycle P1, P2, P3, P4, P5 and P9 reaction conditions.

TABLE 12 Fines accumulation and average CO₂ capture under Cycle P1, P2,P3, P4, P5 and P9 reaction conditions. Calcination 2 5 8 10 13 22 41 5364 76 Cycle P1 <150 μm-% 3.2 6.5 7.4 7.5 Av. % CO₂ Capture 54 57 58 47Cycle P2 <150 μm-% 3.4 3.2 2.9 2.7 3 Av. % CO₂ Capture 72 52 48 45 54Cycle P5 <150 μm-% 5.5 5 6.5 8 Av. % CO₂ Capture 58 46 57 51 Cycle P3<150 μm-% 9.5 10 Av. % CO₂ Capture 75 63 51 Cycle P4 <150 μm-% 10.8 ≈60-≈60- Av. % CO₂ Capture 80 80 Cycle P9 <150 μm-% 2.5 Av. % CO₂ Capture

Cycles P1, P2 and P4 all utilized the same sorbent material. Comparisonof the data for these reaction conditions in Table 12 shows that theCycle P2 reaction conditions, in which the reaction sequence includedintermittent hydration (every three calculations) followed by themodified dehydration step, greatly reduced the sorbent fragmentationwhile maintaining high CO₂ capture capacity.

Although the Cycle P4 reaction conditions, in which the reactionsequence includes periodic hydration, provided improved CO₂ captureactivity compared to Cycle P5, in which the reaction sequence includesintermittent hydration (every three calcinations) followed by themodified dehydration step, the amount of fines produced after only 8calcinations under Cycle P4 reaction conditions exceeded the amountproduced after 76 calcinations under Cycle P5 reaction conditions.

The average CO₂ capture activity of the sorbent under Cycle P1 and CycleP3 reaction conditions, in which the reaction sequence includesintermittent hydration (hydration every three carbonations), wascomparable to that under Cycle P2, Cycle P5 and Cycle P9 reactionconditions, in which the reaction sequence included intermittenthydration (every three calcinations) followed by the modifieddehydration step. Although the Observed degree of fragmentation varieswith the source of the sorbent material, the fragmentation was reducedunder Cycle P2, Cycle P5 and Cycle P9 reaction conditions compared toCycle P1, Cycle P3 and Cycle P4 reaction conditions.

Most of the fragmentation was observed to appear during the first fewreaction cycles under Cycle P2, Cycle P5 and Cycle P9 reactionconditions, in which the reaction sequence included intermittenthydration (every three calcinations) followed by the modifieddehydration step and the rate of fragmentation is greatly reducedthereafter, at least until the seventieth reaction cycle.

Further Experiments on the Modified Dehydration Step

The experiments under Cycle 8, Cycle P2, Cycle P5 and Cycle P9 reactionconditions demonstrated that the modified dehydration step significantlyreduced the fragmentation rate of the sorbent when compared to theconventional dehydration step.

The modified dehydration step follows the hydration of the CaO toCa(OH)₂. In all of the experiments described above, the modifieddehydration step comprised heating the Ca(OH)₂ under a flow of N₂ andCO₂ (20%) to 520° C. and holding at that temperature for 22 minutes.After this step, normal cycling was resumed with a carbonation, in whichthe temperature was raised to 620° C. under a flow of N₂ and CO₂ (20%).

The following experiments, performed in the small reactor, furtherinvestigated the modified dehydration step.

In the first experiment, a bed of freshly hydrated Ca(OH)₂ was heated to520° C. under a flow of N₂ and that temperature was held for 23 minutes.FIG. 9 shows the variation with time of the temperature of the bed andthe vapor pressure of water vapor leaving the bed. At time, equal to 35minutes the vapor pressure was that of the flow of water introduced intothe bed to hydrate CaO to Ca(OH)₂. The water flow was stopped at timeequal to 43 minutes. As the temperature of the bed increased, the vaporpressure of the water vapor leaving the bed showed a sudden increase at445° C. This increase was attributed to the dehydration of the Ca(OH)₂,which took about 6 minutes to complete.

The CaO formed from the dehydration of the Ca(OH)₂ was subsequentlycarbonated in a stream of N₂ and CO₂ (20%) at 620° C. The resultingmaterial was then calcined and the CO₂ capture capacity of the CaO wasmeasured at about 71% of the total capacity.

In the second experiment, a bed of freshly hydrated Ca(OH)₂ was heatedto 620° C. under a flow of N₂ and CO₂ (20%), the temperature being heldat 520° C. for 22 minutes and at 620° C. for 23 minutes. FIG. 10 showsthe variation with time of the temperature of the bed and the vaporpressure of water vapor leaving the bed. At time equal to 35 minutes thevapor pressure was that of the flow of water introduced into the bed tohydrate CaO to Ca(OH)₂. The water flow was stopped at time equalto 43minutes. As the temperature of the bed increased, the vapor pressure ofthe water vapor leaving the bed showed a sudden increase at 618° C. Thisincrease was attributed to the dehydration of the Ca(OH)₂, which tookabout 6 minutes to complete.

Surprisingly, dehydration in the presence of CO₂ occurs only when thesolid reached 618° C. The thermodynamically predicted vapor pressure ofwater in equilibrium with CaO at 600° C. is 4 atm, The Ca(OH)₂ wasexpected to have completed dehydration at much lower temperatures, asshown in the first experiment.

The resulting material was calcined and the CO₂ capture capacity of theCeO was measured at about 58% of the total capacity.

In the third experiment, a bed of freshly hydrated Ca(OH)₂ was heated to520° C. under a flow of N₂ and CO₂ (20%) and held at that temperature.The solid was then heated to 620° C. under a flow of N₂ and held at thattemperature for 22 minutes.

FIG. 11 shows the variation with time of the temperature of the bed andthe vapor pressure of water vapor leaving the bed.

The resulting material was then calcined. It was determined, from theamount of CO₂ released, that 15% of the material was calcium carbonate.This material must have formed in the presence of CO₂ while the materiallargely comprised Ca(OH)₂. This experiment illustrates that Ca(OH)₂ doesnot react with CO₂, or only reacts very slowly with CO₂.

Discussion

In the experiment depicted in FIG. 1I, most of Ca(OH)₂ dehydrated whenthe flow of N₂ and CO₂ (20%) was replaced with a flow of N₂. Acomparison of the experiment shown in FIG. 9 and that shown in FIG. 10shows that the time necessary to dehydrate the Ca(OH)₂ was the same,whether or not CO₂ was present in the gas flow. It appears that theabsorption of CO₂ does not cause the displacement of H₂O, and thatdehydration is the controlling process. Carbonation can only start whenthe Ca(OH)₂ is dehydrated, so that CaO and not Ca(OH)₂ is carbonated. Itappears that carbonation and dehydration are separate processes and donot occur simultaneously.

It appears that the CO₂ in the gas flow inhibits dehydration of theCa(OH)₂ and enables the formation of “superheated” (thermodynamicallyunstable) Ca(OH)₂, which is largely unable to establish thermodynamicequilibrium by losing water.

Ca(OH)₂ Decomposition Temperature

To further examine the effect of CO₂ concentration on the dehydrationtemperature of Ca(OH)₂, five separate experiments were performed inWhich a bed of freshly hydrated Ca(OH)₂ was heated to 520° C. under aflow of N₂ and CO₂ (12.5%, 25%, 37.5%, 70%, and 100%), the temperaturebeing held at 520° C. for 22 minutes and at 620° C. for 23 minutes. Asthe temperature of the bed increased, the water vapor pressure of thegas leaving the bed showed a sudden increase at:

-   -   529° C. for the 12.5% CO₂/N₂ mixture;    -   543° C. for the 25% CO₂/N₂ mixture;    -   611° C. for the 37.5% CO₂/N₂ mixture;    -   519° C. for the 70% CO₂/N₂ mixture; and    -   620° C. for 100% CO₂ gas.

The observed increase in the water vapor pressure of the gas leaving thebed was attributed to the dehydration of the Ca(OH)₂, which took about 6minutes to complete. FIG. 12 shows that the temperature at which thedehydration of Ca(OH)₂ starts increases as the percentage of CO₂ in theenveloping gas increases.

Resistance to Attrition and Ca(OH)₂ Decomposition Temperature

The material formed from the dehydration of Ca(OH)₂ at elevatedtemperatures under a 37.5% CO₂/N₂ mixture showed improved resistance toattrition during calcination/carbonation cycling in a fluidized bed.

Three similar attrition experiments were performed in which Ca(OH)₂ wasdecomposed under a flow of: N₂ (0% CO₂); a 10% CO₂/N₂ mixture; and CO₂.These experiments were performed using the same reaction sequence asCycle P2, and the attrition rates were measured in the same way—bymeasuring the proportion of particles with a size <150 μm at the end ofthe cycling experiment, whether the particles elutriated from thefluidized bed or not. The results of these experiments, and theircomparison with the experiment using a 37.5% CO₂/N₂ mixture, are shownin Table 13.

TABLE 13 Effect of CO₂ concentration during Ca(OH)₂ dehydration onfragmentation and CO₂ capture. % Fragmentation after % CO₂ CaptureExperiment % CO₂ 10 Calcinations 19 Calcinations Activity P2-25 100 2.43.2 50% P2-16 37.5 3 3.6 37% P2-24 10 4.2 5.4 35% P2-6 0 5 6.1 38%

The data in Table 13 show that rate of fragmentation of CaO particlessubject to successive calcination/carbonation cycles in a fluidized bedis significantly reduced by the use of the modified dehydration step, inwhich the Ca(OH)₂ is dehydrated in an atmosphere comprising CO₂. Thedata in FIG. 12 and Table 13 together show that the higher thedehydration temperature of Ca(OH)₂ the lower the rate of fragmentationof CaO particles in subsequent calcination/carbonation cycles.

The data in Table 14 show the effect of the modified dehydration step onthe performance of the CaO sorbent. In Table 14, “None” is acalcination/carbonation cycling process with no hydration ordehydration, “Normal” refers to a calcination/carbonation cyclingprocess which includes intermittent hydration but with no CO₂ presentduring the dehydration step, and “Modified” refers to acalcination/carbonation cycling process which includes intermittenthydration with 100% CO₂ present during the dehydration step.

TABLE 14 Effect of reactivation process on fragmentation and CO₂capture. % Fragmentation after % CO₂ 10 Capture Experiment Dehydrationtype Calcinations 19 Calcinations Activity P2-30 None 0.6 1.3 25% P2-6Normal (No CO₂) 5 6.1 38% P2-25 Modified (100% 2.4 3.2 50% CO₂)

The experiment using a modified dehydration step, with 100% CO₂,provided superior CO₂ capture activity after 19 calcination/carbonationcycles compared to the other experiments and the rate of attrition wasmuch lower than the experiment using a conventional dehydration step,during which there is no CO₂ present.

“Hold time”

Two experiments were performed using the same reaction sequence as CycleP2, using the modified dehydration step with a 37.5% CO₂/N₂ mixture butwith a hold time at 520° C. of zero minutes for one and 40 minutes forthe other. The resulting samples where then subjected to multiplecarbonation/calcination cycles and analyzed for particle size and CO₂absorption activity as described above. The results are shown in Table15.

TABLE 15 Effect of “hold time” on fragmentation and CO₂ capture. %Fragmentation after Hold time 10 % CO₂ Capture Experiment (mins)Calcinations 19 Calcinations Activity P2-34 40 2.2 2.6 42% P2-31 23 3.44.1 31% P2-32 0 4.7 5.8 45%

The data in Table 15 show that an increase in the time spent by theCa(OH)₂ at 520° C. under a 37.5% CO₂/N₂ mixture substantially reducedthe attrition rate, while maintaining CO₂ absorption activity,

Hydration Conditions

Experiments were conducted using different amounts of water vapor in thegas used to form Ca(OH)₂ from freshly prepared CaO. The experiments wereperformed using the same reaction sequence as Cycle P2, using themodified dehydration step with a 37.5% CO₂/N₂ mixture, but the amount ofwater injected into the reactor was varied. The results are shown inTable 16.

TABLE 16 Effect of absolute humidity levels on fragmentation and CO₂capture. % Fragmentation after Absolute 10 % CO₂ Capture ExperimentHumidity Calcinations 19 Calcinations Activity P2-12 27% 3.5 5.5 48%P2-16 34% 3.0 3.6 37% P2-40 43% 2.4 4.6 38%

The data in Table 16 show that, in the absolute humidity range from 27%to 43%, the fragmentation rate was lower than that for reactionsincluding hydration but with no CO₂ present during the dehydration step(see Table 14). In addition, the CO₂ absorption activity was higher thanthat observed when no hydration/dehydration is used. This data showsthat the efficacy of the hydration/dehydration process for restoring CO₂absorption activity is not strongly dependent on the absolute humiditylevel during the formation of Ca(OH)₂.

Further experiments were conducted to examine the effect of hydrationtemperature on the rate of fragmentation and the CO₂ absorption activityduring calcination/carbonation. The results are shown in Table 17,

TABLE 17 Effect of hydration temperature on fragmentation and CO₂capture. Hydration % Fragmentation after Temperature 10 19 % CO₂ CaptureExperiment (° C.) Calcinations Calcination Activity P2-8 361-374 3.7 4.444% P2-12 312-329 3.5 5.5 48% P2-4 340-400 4.3 4.4 38%

The data in Table 17 show that the rate of fragmentation is unaffectedby hydration temperatures in the range of 312° C.-400° C. However, CO₂absorption activity is favored by the lower temperature range forhydration of 312° C.-329° C.

Temperature Profile

A first cycling experiment was performed using the same reactionsequence as Cycle P2 but with a variation of the modified dehydrationstep. In this experiment, a bed of freshly hydrated Ca(OH)₂ was heatedat a constant rate of temperature increase of about 13° C./minute up to620° C. under a flow of N₂ and CO₂ (37.5%). This modified dehydrationstep was followed by normal carbonation/calcination cycling as describedabove and the sorbent analyzed for fragmentation rate and CO₂ absorptionactivity. The data is presented in Table 18 as Experiment P2-41.

In a second cycling experiment, the bed of freshly hydrated Ca(OH)₂ washeated to 520° C. under a flow of N₂ and CO₂ (37.5%) and held for 23minutes at that temperature. This modified dehydration step was followedby normal carbonation/calcination cycling as described above and thesorbent analyzed for fragmentation rate and CO₂ absorption activity. Thedata is presented in Table 18 as Experiment P2-31.

In Table 18, Experiments P2-41 and P2-31 are compared with the “Normal”cycle, which includes hydration but with no CO₂ present during thedehydration. Both Experiments produce a sorbent that has a higherresistance to attrition than the conventional hydration process in whichno CO₂ is present during the dehydration.

TABLE 18 Effect of temperature profile on fragmentation and CO₂ capture.% Fragmentation after % CO₂ 10 Capture Experiment Variant Calcinations19 Calcinations Activity P2-6 Normal (No CO₂) 5 6.1 38% P2-41 No hold 24.7 37% P2-31 Hold at 520° C. 3.4 4.1 31%

Heat Up Rate

An experiment was performed using the conditions described above forExperiment P2-41 but in which the constant rate of temperature increaseof the bed of freshly hydrated Ca(OH)₂ was about 40° C./minute up to620° C. The data are included in Table 19, together with those forExperiment P2-41. The data show that the heat up rate affects the rateof fragmentation during subsequent calcination/carbonation cycles onlyfor about 10 calcinations. Also, an increased heat up rate appears toprovide higher CO₂ absorption activity.

TABLE 19 Effect of heat up rate on fragmentation and CO₂ capture. %Fragmentation after Heat up rate 10 19 % CO₂ Capture Experiment (°C./min) Calcinations Calcinations Activity P2-32 40 4.7 5.8 45% P2-41 132 4.7 37%

Stopping CO₂ Flow

A first cycling experiment was performed using the same reactionsequence as Cycle P2 but with a variation of the modified dehydrationstep. In this experiment, a bed of freshly hydrated Ca(OH)₂ was heatedto 520° C. under a flow of N₂ and CO₂ (37.5%). The temperature was heldat 520° C. for 23 minutes. Instead of continuing with normalcarbonation/calcination cycling, the CO₂ supply was abruptly terminatedand only N₂ continued to flow. The solid was held at 520° C. under aflow of N₂ for 22 more minutes. Within a minute of the CO₂ supply beingterminated, the humidity sensor recorded a significant increase in wateroutflow from the reactor indicating that the Ca(OH)₂ had substantiallydehydrated. The newly formed CaO was then subjected to normalcarbonation/calcination cycling as described above and analyzed forfragmentation rate and CO₂ absorption activity. The data are presentedin Table 20 as Experiment P2-5.

In a second cycling experiment, the bed of freshly hydrated Ca(OH)₂ washeated to 520° C. under a flow of N₂ and CO₂ (37.5%) and held at thattemperature for 23 minutes. Normal carbonation/calcination cycling asdescribed above was then performed and the sorbent analyzed forfragmentation rate and CO₂ absorption activity. The data are presentedin Table 20 as Experiment P2-16.

TABLE 20 Effect of stopping CO₂ flow on fragmentation and CO₂ capture. %Fragmentation after % CO₂ 10 Capture Experiment Variant Calcinations 19Calcinations Activity P2-5 Remove CO₂ 4.2 4.7 36% P2-16 Maintain CO₂ 33.6 38% P2-6 Normal (No CO₂) 5 6.1 38%

The data show that maintaining the CO₂ during the dehydration of Ca(OH)₂produces a lower fragmentation rate during multiplecalcination/carbonation cycles in a fluidized bed than does removing theCO₂ during dehydration. Both experiments produced a sorbent that has ahigher resistance to attrition than the equivalent experiment in whichno CO₂ was present during the dehydration step.

Discussion

The inhibition of the dehydration of Ca(OH)₂, as shown by an increaseddecomposition temperature, is an increasing function of theconcentration of CO₂ in the enveloping gas as shown in FIG. 12.

CaO that has been formed by dehydrating Ca(OH)₂ has been shown to haverestored ability of the resulting CaO to react with CO₂ gas throughoutseveral cycles. However, dehydration performed in the absence of CO₂gas, or at minimal CO₂ concentration, results in CaO particles that areweakened and suffer increased attrition in a fluidized bed. Dehydrationof Ca(OH)₂ performed in the presence of CO₂, and particularly when theCO₂ concentration is above 10% by mass, provides CaO particles that aremore resistant to attrition in a fluidized bed.

Conclusions

Hydrating CaO restores its capacity to capture CO₂ after severalcalcination/carbonation cycles, but also induces substantialfragmentation which limits the practical application of this method.Intermittent hydration reduces sorbent fragmentation compared toperiodic hydration, but the fragmentation levels remain significant.Unsurprisingly, the source of the sorbent did not affect the activitylevels throughout the reaction cycles. It appears that the processconditions, in particular the frequency of hydration, are the maincontrolling factor of the CO₂ capture activity.

Intermittent hydration using a dehydration step in the presence of CO₂maintains high physical strength of the sorbent while at the samemaintaining high CO₂ capture capacity. Dehydrating Ca(OH)₂ in thepresence of CO₂ leads to dehydration taking place at a highertemperature than that which is observed for dehydration under N₂ only.This enables CO₂ capture cycling with a sorbent that retains physicalactivity (no fragmentation) and chemical activity (high CO₂ capturepercentage) throughout many cycles.

It is not the intention to limit the scope of the invention to theabovementioned examples only. As would be appreciated by a skilledperson in the art, many variations are possible without departing fromthe scope of the invention as set out in the accompanying claims.

1. A process for restoring the ability of an alkaline earth metal oxideto react with CO₂, wherein the alkaline earth metal oxide is used in acyclic process, wherein the alkaline earth metal oxide is reacted withCO₂ to form an alkaline earth metal carbonate and the alkaline earthmetal carbonate is calcined to regenerate the alkaline earth metaloxide, the process comprising the steps of: (a) contacting the alkalineearth metal oxide with water to form an alkaline earth metal hydroxide;(b) heating the alkaline earth metal hydroxide in a first gas stream,wherein the first gas stream comprises CO₂, to a temperature higher thanthe normal dehydration temperature for the alkaline earth metalhydroxide; and (c) dehydrating the alkaline earth metal hydroxide toregenerate the alkaline earth metal oxide.
 2. A process as claimed inclaim 1, wherein, in step (b), the alkaline earth metal hydroxide isheated in the first gas stream comprising CO₂ to a temperature and for atime and at a concentration of CO₂ effective to suppress the dehydrationof the alkaline earth metal hydroxide and reduce the attrition andfragmentation rates, compared to those that would otherwise occur, ofthe alkaline earth metal oxide formed upon dehydration of the alkalineearth metal hydroxide.
 3. A process as claimed in claim 1, wherein thealkaline earth metal oxide is contacted with water vapor to form thealkaline earth metal hydroxide.
 4. A process as claimed in claim 3,wherein the alkaline earth metal oxide is contacted with water vapor atan absolute humidity from 5% to 100%.
 5. A process as claimed in claim3, wherein the alkaline earth metal oxide is contacted with water vaporat an absolute humidity from 30% to 43%.
 6. A process as claimed, inclaim 3, wherein the alkaline earth metal oxide is contacted with watervapor at a temperature from 100° C. to 400° C.
 7. A process as claimedin claim 1, wherein the first gas stream comprises 20% to 100% CO₂.
 8. Aprocess as claimed in claim 1, wherein the first gas stream comprises30% to 100% CO₂.
 9. A process as claimed in claim 1, wherein the firstgas stream comprises 37.5% to 100% CO₂.
 10. A process as claimed inclaim 1, wherein the temperature in step (b) is at least about 50° C.higher than the normal decomposition temperature for the alkaline earthmetal hydroxide.
 11. A process as claimed claim 1, wherein thetemperature in step (b) is from 500° C. to 600° C.
 12. A process asclaimed in claim 1, wherein the temperature in step (b) is maintainedconstant for a period of time.
 13. A process as claimed in claim 1,wherein the total time spent by the alkaline earth metal hydroxide at atemperature that is higher than the normal decomposition temperature forthe alkaline earth metal hydroxide is at least about 10 minutes.
 14. Aprocess as in claim 1, wherein the alkaline earth metal hydroxide isheated to a temperature from 500° C. to 800° C. to dehydrate thealkaline earth metal hydroxide and regenerate the alkaline earth metaloxide.
 15. A process as claimed in claim 1, wherein the alkaline earthmetal hydroxide is dehydrated in a second gas stream to regenerate thealkaline earth metal oxide.
 16. A process as claimed in claim 15,wherein the concentration of CO₂ in the second gas stream results indehydration of the alkaline earth metal hydroxide at the temperature atwhich the second gas stream substitutes for the first gas stream.
 17. Aprocess as claimed in claim 1, wherein at least one step of the processis performed in one or more fluidized or moving bed.
 18. A process asclaimed in any claim 1, wherein the alkaline earth metal oxide isselected from: CaO; MgO; and mixtures thereof.
 19. A process as claimedin claim 1, wherein the alkaline earth metal oxide is CaO.
 20. A processas claimed in claim 1, wherein the alkaline earth metal oxide retains anaverage CO₂ absorption capacity of at least about 40%, measured withrespect to the initial capacity, after 75 calcinations.